CN112300490A - 一种微发泡聚丙烯复合材料及其制备方法和应用 - Google Patents
一种微发泡聚丙烯复合材料及其制备方法和应用 Download PDFInfo
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- 239000004743 Polypropylene Substances 0.000 title claims abstract description 78
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 76
- -1 polypropylene Polymers 0.000 title claims abstract description 73
- 238000005187 foaming Methods 0.000 title claims abstract description 55
- 239000002131 composite material Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000011347 resin Substances 0.000 claims abstract description 20
- 229920005989 resin Polymers 0.000 claims abstract description 20
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 14
- 239000000945 filler Substances 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 18
- 239000000155 melt Substances 0.000 claims description 15
- 239000004088 foaming agent Substances 0.000 claims description 11
- 238000001746 injection moulding Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 239000011159 matrix material Substances 0.000 claims description 6
- 239000003963 antioxidant agent Substances 0.000 claims description 5
- 230000003078 antioxidant effect Effects 0.000 claims description 5
- 239000004611 light stabiliser Substances 0.000 claims description 5
- 229920005629 polypropylene homopolymer Polymers 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229920001684 low density polyethylene Polymers 0.000 claims description 4
- 239000004702 low-density polyethylene Substances 0.000 claims description 4
- 239000000049 pigment Substances 0.000 claims description 4
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- 238000001125 extrusion Methods 0.000 claims description 3
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- 239000000314 lubricant Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 239000000454 talc Substances 0.000 claims description 2
- 229910052623 talc Inorganic materials 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims 1
- 239000006260 foam Substances 0.000 abstract description 7
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- 238000002347 injection Methods 0.000 description 8
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- 230000000052 comparative effect Effects 0.000 description 7
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000004697 Polyetherimide Substances 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical group [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
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- 210000000497 foam cell Anatomy 0.000 description 2
- 229920001601 polyetherimide Polymers 0.000 description 2
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- SSADPHQCUURWSW-UHFFFAOYSA-N 3,9-bis(2,6-ditert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C)=CC(C(C)(C)C)=C1OP1OCC2(COP(OC=3C(=CC(C)=CC=3C(C)(C)C)C(C)(C)C)OC2)CO1 SSADPHQCUURWSW-UHFFFAOYSA-N 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
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- 230000005540 biological transmission Effects 0.000 description 1
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- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
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- 150000002148 esters Chemical class 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- HNMCSUXJLGGQFO-UHFFFAOYSA-N hexaaluminum;hexasodium;tetrathietane;hexasilicate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].S1SSS1.S1SSS1.[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] HNMCSUXJLGGQFO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- YOBAEOGBNPPUQV-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe].[Fe] YOBAEOGBNPPUQV-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
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- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 230000008054 signal transmission Effects 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/08—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing carbon dioxide
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0066—Use of inorganic compounding ingredients
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- C08J2205/044—Micropores, i.e. average diameter being between 0,1 micrometer and 0,1 millimeter
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- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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Abstract
本发明公开了一种微发泡聚丙烯复合材料及其制备方法和应用,包括组分:聚丙烯树脂60~98份;POE0‑30份;填料0~30份;发泡母粒0.5‑5份;所述微发泡聚丙烯复合材料为内部具有均匀泡孔,外部具有密实皮层的“三明治”皮芯结构。本发明所制备的微发泡聚丙烯复合材料为内部具有均匀泡孔,外部具有密实皮层的“三明治”皮芯结构,具有更低的介电常数,在汽车保险杠装饰板、牌照装饰板、门板装饰板等应用中有较好的前景,为未来汽车自动驾驶领域、5G领域的进一步应用提供支持。
Description
技术领域
本发明属于高分子材料领域,具体涉及一种微发泡聚丙烯复合材料及其制备方法和应用。
背景技术
聚丙烯作为一种高性价比的通用塑料,通过改性后具有高强度高韧性的优秀力学性能及耐化学品性,电绝缘性优良,具有很好的可塑性,广泛的应用于汽车内外饰产品中。
专利CN111073148A中公开了一种低介电常数微发泡玻纤增强聚丙烯复合物及其制备方法,采用四氟乙烯作为增粘剂提高熔体粘度,有利于发泡过程的进行,得到的聚丙烯复合物具有低密度、高强度、低介电常数等特点,是一类非常适用于5G产品的材料,特别是5G 基站天线罩等类似应用,这种玻纤增强聚丙烯主要是应用于结构零件,由于其外观质量稍差,限制其在具有较好外观的装饰件上的应用。随着5G技术的发展,更低介电常数且兼具外观与信号传递功能的装饰件显得尤为必要。
CN110437540 A公开了其制得的改性PP材料介电常数低、高强度、耐候性好,恶劣环境下仍能保持良好的介电性能、机械性能、阻燃性能和尺寸稳定性,其通过聚醚酰亚胺(PEI)以及玻纤的加入提升聚丙烯材料的强度,其主要应用领域在结构件以及高温连接件等等。
因此本领域尚需开发一种非玻纤增强、制备简单且能有效适用于汽车装饰零件,既满足汽车对材料轻量化的要求,同时具有更低介电常数的聚丙烯复合材料,为未来汽车自动驾驶领域、5G领域的进一步应用提供支持。
发明内容
为了克服上述现有技术存在的不足,本发明的首要目的在于提供一种微发泡聚丙烯复合材料,该微发泡聚丙烯复合材料具有更低的介电常数。
本发明的另一目的在于提供上述微发泡聚丙烯复合材料的制备方法。
本发明是通过以下技术方案实现的:
一种微发泡聚丙烯复合材料,按重量份数计,包括以下组分:
聚丙烯树脂 60~98份;
POE 0~30份;
填料 0~30份;
发泡母粒 0.5-5份;
本发明制备得到的微发泡聚丙烯复合材料为内部具有均匀泡孔,外部具有密实皮层的“三明治”皮芯结构。本发明通过研究发现,微发泡聚丙烯复合材料的内部泡孔密度是影响介电常数的主要因素之一,介电常数随着泡孔密度的增加而降低,优选的,所述微发泡聚丙烯复合材料内部的泡孔密度至少为3*106个/cm3,优选至少为10*106个/cm3。
优选的,所述聚丙烯树脂为均聚聚丙烯、嵌段共聚聚丙烯或无规共聚聚丙烯中的一种或几种的混合。
本发发明通过研究发现,不同熔体质量流动速率的聚丙烯树脂影响复合材料的发泡效果。
优选的,所述聚丙烯树脂在230℃,2.16 Kg负荷下的熔体质量流动速率为30~100g/10min,更优选熔体质量流动速率为30~40g/10min、熔体质量流动速率为50~70g/10min及熔体质量流动速率为80~100g/10min的三种不同熔体质量流动速率的聚丙烯树脂的复配物。研究结果表明,采用三种不同流动性的聚丙烯树脂复配的复合材料具有更好的发泡效果,泡孔数量明显增加,从而使复合材料的介电常数明显降低。优选的,所述POE为乙烯辛烯共聚物,POE的添加明显提升整个体系的熔体强度,泡孔不易破裂,泡孔密度更高,在230℃,2.16 Kg负荷下,其熔体质量流动速率为0.1~30 g/10min。
优选的,所述填料选自碳酸钙、滑石粉中的一种或两者的混合物,所述填料的粒径为3000目或以上。
优选的,所述发泡母粒包括基体和发泡剂,其中所述基体为LDPE,所述发泡剂选自碳酸氢盐类(如碳酸氢钠)、柠檬酸盐类(如柠檬酸钠)中的一种或者几种的混合物,其中发泡剂的重量含量占发泡母粒的10-50%。如果发泡剂含量过低,发气量不足导致零件无法充满,影响泡孔密度,如发泡剂含量太多,则会出现局部发气剧烈从而出现大量并孔,影响泡孔密度。
根据实际性能需要,本发明所述的微发泡聚丙烯复合材料,按重量份数计,还包括0-2份颜料、0-3份助剂,所述助剂为抗氧剂、光稳定剂或润滑剂中的一种或几种的混合。
所述抗氧剂为受阻酚类或亚磷酸酯类抗氧剂,具体可以是1010、1076、3114、168、PEP-36中的一种或者两种及以上的混合物;
所述光稳定剂为受阻胺类光稳定剂,具体可以是UV-3808PP5、LA-402XP、LA-402AF中的一种或者两种及以上的混合物;
所述润滑剂为硅酮类、酰胺类、聚丙烯类、硬脂酸类、脂肪酸及酯类中的一种或者两种及以上的混合物;
所述颜料为炭黑、酞青蓝、酞青绿、铁红、铁黄、群青紫其中一种或者几种的混合物;
本发明还提供了上述的微发泡聚丙烯复合材料的制备方法,包括如下步骤:
(1)将聚丙烯树脂、POE、填料混合均匀后加入双螺杆挤出机中,进行熔融混炼,熔融混炼温度为170~220℃,螺杆转速为350~450转/分,挤出造粒,得到聚丙烯组合物;
(2)将聚丙烯组合物与发泡母粒混合后加入到注塑机中,于190-220℃条件下采用闭模或二次开模工艺注塑成型,得到微发泡聚丙烯复合材料。
本发明所述的闭模工艺与开模工艺需要符合注塑机含有闭锁射嘴,以及机台的最大射速能达到200mm/s以上。所述闭模工艺是将发泡母粒与聚丙烯组合物混合后加入到注塑机料斗中,注塑时采用欠注方式预留一定的型腔空间,发泡母粒在射嘴喷出,压力释放后产生气体,从而使得熔体膨胀实现进一步定型的过程。所述二次开模工艺将发泡母粒与聚丙烯组合物混合后加入到注塑机料斗中,注塑时采用满注的方式完全充满空间,满注时零件的厚度称之为初始厚度,充满完成后模具后退一段距离定型到模具的最终厚度并冷却完成定型。
步骤(2)中,所述二次开模工艺中模具的厚度为2.1-3.0mm,2.1mm为模具初始厚度,3.0mm为模具的最终厚度。
本发明还提供了上述的微发泡聚丙烯复合材料在汽车内外装饰件中的应用,在汽车保险杠装饰板、牌照装饰板、门板装饰板等应用中有较好的前景。
与现有技术相比,本发明具有如下有益效果:
本发明所制备的微发泡聚丙烯复合材料为内部具有均匀泡孔,外部具有密实皮层的“三明治”皮芯结构,在满足汽车对材料轻量化的要求的基础上,同时具有更低介电常数,在汽车保险杠装饰板、牌照装饰板、门板装饰板等应用中有较好的前景,为未来汽车自动驾驶领域、5G领域的进一步应用提供支持。
本发明的制备方法简单、便于实行,相比玻纤填充材料的介电常数有非常明显的降低,能有效应用汽车内外饰零件上。
具体实施方式
下面结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明,单不以任何形式限制本发明。应当指出的是,对本领域的普通技术人员来说,在不脱离本发明构思的前提下,还可以做出若干变形和改进。这些都属于本发明的保护范围。
本发明实施例及对比例所用的原材料均来源于市购,但不限于这些材料:
聚丙烯1:均聚聚丙烯,熔体质量流动速率MFR(230℃/2.16 Kg)为30g/10min,市售;
聚丙烯2:均聚聚丙烯,熔体质量流动速率MFR(230℃/2.16 Kg)为50g/10min,市售;
聚丙烯3:均聚聚丙烯,熔体质量流动速率MFR(230℃/2.16 Kg)为100g/10min,市售;
POE:乙烯辛烯共聚物,熔体质量流动速率MFR(230℃/2.16 Kg)为16g/10min,市售;
填料:
滑石粉:市售,粒径为3000目;
玻璃纤维:市售,短切玻璃纤维,平均长度为10mm,纤维平均直径2μm;
发泡母粒1:基体为LDPE,发泡剂为碳酸氢钠,发泡剂的重量含量占发泡母粒的35%,市售;
发泡母粒2:基体为LDPE,发泡剂为碳酸氢钠,发泡剂的重量含量占发泡母粒的5%,市售;
颜料:炭黑,市售;
抗氧剂:抗氧剂1010,市售;
光稳定剂:UV-3808PP5,市售。
实施例1-10与对比例1-3:
按表1-2配方,将聚丙烯树脂、POE、填料混合均匀后加入双螺杆挤出机中,进行熔融混炼,熔融混炼温度为170~220℃,螺杆转速为350~450转/分,挤出造粒,得到聚丙烯组合物;
将聚丙烯组合物与发泡母粒混合后加入到注塑机中,于210℃条件下采用闭模或二次开模工艺注塑成型,得到微发泡聚丙烯复合材料。
其中,实施例1-2和对比例1-3采用闭模工艺注塑成100*100*3mm闭模发泡样片;
实施例3-15采用二次开模工艺注塑成100mm*100mm*3mm开模发泡样片,二次开模工艺中模具的厚度为2.1-3.0mm,2.1mm为模具初始厚度,3.0mm为模具的最终厚度。
各性能测试方法:
泡孔密度:利用二次元影像测量仪观察缺口冲击后的PP发泡样品的断面形貌。利用Image-Pro软件对获得的二次元图片进行处理,统计泡孔数量、平均泡孔直径以及泡孔尺寸分布,测量与注塑模具静模面接触的发泡样品的皮层厚度。统计的泡孔个数大于100个;泡孔尺寸是发泡样品泡孔的平均直径;泡孔密度N0是发泡样品每立方厘米中泡孔的个数,按照公式(1)、(2)进行计算:
其中,N0为泡孔密度,个/cm3;n为统计面积中泡孔个数;M为电镜照片放大倍数;A为电镜照片中所选择的统计面积,cm2;Vf为发泡样品中气体所占的比例;ρf为发泡样品的密度,g/cm3;ρ为未发泡样品的密度,g/cm3。
介电常数DK:使用Keysight N5225A矢量网络分析仪设置频率76-77GHz采用传输线反射法对样片的介电常数进行测试。
表2:实施例10-15及对比例1-3中各组分的含量(重量份)
从对比例1和对比例3对比可以发现,添加滑石粉相比添加玻璃纤维更能降低材料的介电常数;通过实施例1、2与对对比例2、3的比较,材料通过闭模发泡后泡孔密度在3*106个/cm3以上,闭模发泡后的样片介电常数明显比发泡前小的多,说明闭模发泡泡孔密度的增加降低了材料的介电常数;通过实施例1、2对比,实施例3、4对比,可以发现复合材料中添加滑石粉比不添加滑石粉的发泡泡孔更多,泡孔里的气体是更低的介电常数介质,因此介电常数随着泡孔的增加而降低;通过实施例1、3对比,实施例2、4对比,采用二次开模工艺获得的发泡样片,泡孔数量远远大于闭模发泡样片的泡孔数量,因此样片的发泡层占比更大,介电常数更低;实施例3与实施例5-7对比发现,采用三种不同流动性的聚丙烯树脂复配的复合材料具有更好的发泡效果,泡孔数量几乎两倍于实施例5-7,介电常数明显降低。
Claims (10)
1.一种微发泡聚丙烯复合材料,其特征在于,按重量份数计,包括以下组分:
聚丙烯树脂 60~98份;
POE 0~0份;
填料 0~30份;
发泡母粒 0.5-5份。
2.根据权利要求1所述的微发泡聚丙烯复合材料,其特征在于,所述微发泡聚丙烯复合材料为内部具有均匀泡孔,外部具有密实皮层的“三明治”皮芯结构,所述微发泡聚丙烯复合材料内部的泡孔密度至少为3*106个/cm3,优选至少为10*106个/cm3。
3.根据权利要求1所述的微发泡聚丙烯复合材料,其特征在于,所述聚丙烯树脂为均聚聚丙烯、嵌段共聚聚丙烯或无规共聚聚丙烯中的一种或几种的混合,所述聚丙烯树脂在230℃,2.16 Kg负荷下的熔体质量流动速率为30~100 g/10min,优选在230℃,2.16 Kg负荷下,熔体质量流动速率为30~40g/10min、熔体质量流动速率为50~70g/10min及熔体质量流动速率为80~100g/10min的三种不同熔体质量流动速率的聚丙烯树脂的复配物。
4.根据权利要求1所述的微发泡聚丙烯复合材料,其特征在于,所述POE为乙烯辛烯共聚物,在230℃,2.16 Kg负荷下,其熔体质量流动速率为0.1~30 g/10min。
5.根据权利要求1所述的微发泡聚丙烯复合材料,其特征在于,所述填料选自碳酸钙、滑石粉中的一种或两者的混合物,所述填料的粒径为3000目或以上。
6.根据权利要求1所述的微发泡聚丙烯复合材料,其特征在于,所述发泡母粒包括基体和发泡剂,所述基体为LDPE,所述发泡剂选自碳酸氢盐类、柠檬酸盐类中的一种或者几种的混合物,其中发泡剂的重量含量占发泡母粒的10-50%。
7.根据权利要求1所述的微发泡聚丙烯复合材料,其特征在于,按重量份数计,还包括0-2份颜料、0-3份助剂,所述助剂为抗氧剂、光稳定剂或润滑剂中的一种或几种的混合。
8.权利要求1-7任一项所述的微发泡聚丙烯复合材料的制备方法,其特征在于,包括如下步骤:
(1)将聚丙烯树脂、POE、填料混合均匀后加入双螺杆挤出机中,进行熔融混炼,熔融混炼温度为170~220℃,螺杆转速为350~450转/分,挤出造粒,得到聚丙烯组合物;
(2)将聚丙烯组合物与发泡母粒混合后加入到注塑机中,于190-220℃条件下采用闭模或二次开模工艺注塑成型,得到微发泡聚丙烯复合材料。
9.根据权利要求8所述的微发泡聚丙烯复合材料的制备方法,其特征在于,步骤(2)中,所述二次开模工艺中模具的厚度范围为2.1-3.0mm,2.1mm为模具的初始厚度,3.0mm为模具的最终厚度。
10.根据权利要求1-7任一项所述的微发泡聚丙烯复合材料在汽车内外装饰件中的应用。
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